CN109738563A - A kind of non-derived detection method of ethylene bisdithiocarbamic salt pesticide - Google Patents
A kind of non-derived detection method of ethylene bisdithiocarbamic salt pesticide Download PDFInfo
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Abstract
The invention discloses a kind of non-derived detection methods of ethylene bisdithiocarbamic salt pesticide.The present invention dissolves EBDCs by the ethylenediamine solution of EDTA, and has good response in mass spectrum, has found the non-derived detection method of EBDCs.Method pre-treatment is simple, without derivatization and Solid Phase Extraction, there is the good rate of recovery, accuracy and the rate of recovery.4 kinds of detection maneb, zineb, Mancozeb, Propineb etc. linear scale relationships in 20~2000ng/ml concentration range for gloomy class compound, related coefficient is 0.9946-0.9999, the rate of recovery is 81.40%~91.01% when pitch-based sphere is 10,20,100 μ g/kg, and relative standard deviation is between 2.89%~4.42%.Method pretreatment simple and sensitive is good, and reproducibility is high, for the quick detection of gloomy pesticide residue suitable for pericarp.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues fields, more particularly, to a kind of ethylene bisdithiocarbamic
The non-derived detection method of salt pesticide.
Background technique
Mancozeb, maneb, zineb, Propineb etc. are ethylene bisdithiocarbamic salt for gloomy class pesticide
(EBDCs) class fungicide.It is insoluble in water for gloomy class, most of organic solvents are not dissolved in, but can be dissolved in pyridine, to light, heat, tide
Moist lability, easily decomposites carbon disulfide, meets the substances such as alkaline matter or copper, mercury and easily decomposes to give off carbon disulfide and reduction,
Volatility is small.Because such fungicide is at low cost, purposes is wide, to people and animals' low toxicity, be still widely used in cereal, vegetables, fruit tree, gloomy so far
The disease control of the plants such as woods.
For studies have shown that in 750mg/kg dosage, rat has hereditary tumor and capsula glandulae thyreoideae cystencyte adenoma and cancer
It is formed；U.S.EPA proves that EBDCs has moderate stimulation to mammal skin and respiratory apparatus with spraying and test of dusting,
Symptoms be itch, sore-throat, airway inflammation etc., without obvious neurotoxicity, but catabolite carbon disulfide is neurotoxin.
After the metabolite ethylene thiourea (ETU) for reporting EBDCs has teratogenesis, carcinogenesis, the toxicity toxicity in relation to EBDCs
Many disputes are caused with environmental behaviour etc..Canadian pest management office (PMRA) suggests being phased out certain purposes
Ethylene bisdithiocarbamic (EBDCs) class fungicide Mancozeb." GB 2763-2014 national food safety standard food
Pesticide maximum residue limit in product " in ten several cereal, veterinary antibiotics, edible mushroom for gloomy amine, Carbatene, Mancozeb,
Four kinds of zineb etc. are limited the quantity for gloomy class, and the limitation of different substrates is 0.5~5mg/kg.It is current studies have shown that Dai Sen
Class pesticide remains essentially on the pericarp of vegetables and fruits, and cleaning process can shift most pesticide residue.
Method of the Europe for detecting EBDCs is to improve Keppel method, this method is to be deposited based on EBDCs in stannous chloride
Carbon disulfide is generated in acid medium under, regenerates IV, IV-bis- (2- hydroxyethyl)-thiocarbamic acid copper (II)
Complex compound is detected on spectrophotometer.The device is complicated for this method, and the operating time is long, poor repeatability.The country is not yet
The national standard method of EBDCs measurement, inlet and outlet industry test stone SN0139-1992 " export dithiocarbamate in cereal
The residual quantity method of inspection ", SN0157-1992 " the dithiocarbamate residual quantity method of inspection in export Fruit ",
The method of SN07111997 " the zineb class pesticide total residue method of inspection in outlet tealeaves " measurement EBDCs is headspace gas color
Spectrometry.The method by sample to be tested in closed system with reduction acid solution reaction, quantitatively release carbon disulfide, take gas on liquid
Body gas Chromatographic Determination wherein carbon disulfide content, reflects the content of EBDCs, but headspace gas chromatography cannot synchronize indirectly
Qualitative analysis is carried out, poor repeatability is easy to produce false positive when measuring the food of sulfur-bearing.
Wherein, the problem detected associated with liquid chromatography mass is to be difficult to ionize for gloomy class.Industry is imported and exported to examine
Standard SN/T 0711-2011 " exports the detection method liquid phase color of dithiocarbamate (salt) pesticide residue amount in tealeaves
Spectrum-mass spectrum/mass spectrography " in, use derivatization liquid chromatography-mass spectrometry.Under room temperature, the EDTA2Na using alkalinity is molten
EBDCs is converted into sodium salt soluble easily in water by liquid, and ion-pairing agent is added, carries out esterification, HLB Solid Phase Extraction with methyl iodide
Column purification, methanol elution, after eluent is concentrated to dryness, -0.1% formic acid solution residue of acetonitrile, liquid chromatography-mass spectrography/mass spectrum is adopted
It is measured with positive ion mode, quantified by external standard method.The method detection limit is low, and precision is reliable.But pre-treatment is related to derivative and solid
It mutually extracts, cumbersome complexity.
It is high to lack a kind of detection accuracy at present in summary, the simple and convenient detection method for gloomy class pesticide.
Summary of the invention
It is a kind of not by the method for derivatization, use the purpose of the invention is to overcome the deficiencies of the prior art and provide
Suitable solvent makes to ionize and have good response, and sensitivity, the rate of recovery of improvement method in mass spectrum for gloomy class
And accuracy, optimal conditions is selected, is obtained suitable for pericarp for the detection method of gloomy class.
The first purpose of the invention is to provide a kind of detection methods of dithiocar-bamate.
A second object of the present invention is to provide application of the method in detection dithiocar-bamate.
To achieve the goals above, the present invention is achieved by the following technical programs:
This method is dissolved EBDCs with 3% ethylenediamine solution containing EDTA2Na, can be ionized in mass spectrum, according to
210.9 quasi-molecular ions is with qualitative and quantitative.The principle of the analysis method is that (Fig. 1): EDTA is a kind of strong metal chelating agent, due to
The complex for forming chelate ring with same metal ion with two or more coordinations forms chelate.Chelating agent is to various metals
Ion selectivity with higher and sensitivity are preferably stablized so the metallo-chelate and similar complex compound that generate have
Property, it is difficult because to simultaneously switch off two keys that chelating agent is coordinated on metal, the chelating with five-membered ring or hexatomic ring
Object is very stable, and the ring formed is more, and chelate is more stable.The EDTA2Na of high concentration can be tearing open for the metal in gloomy class
It opens, grab metal ion and metal ion-chelant；In thiocarboxyl group, due to there is a pair of unshared lone pair electrons in sulphur double bond,
C-S is that have certain tilt angle to be conjugated with sulphur double bond, forms a big pi bond, and the property of two sulphur is identical；In ethylenediamine
In aqueous solution, due to solution alkaline, the free state positive charge in system only has ethylenediamine ion and sodium ion, and sodium is by hydrogen-oxygen
Root surrounds, therefore ethylenediamine and dithiocarboxyl form a relatively steady state, is in betatopic state in ionization；
At a high temperature of mass spectrum, the bonding state of dithiocarboxyl and ethylenediamine becomes unstable, and detection 210.9 ion of m/z becomes
The foundation of the quantitative bisdithiocarbamic ester of this method.Pass through the parent ion of detection EDTA and the chelating of different metal ions
Difference come it is qualitative.Simple and quick, detection limit is low, and precision is good.But maneb, zineb, Mancozeb, Carbatene this
Four kinds of EBDCs fail to get 105 quasi-molecular ions of m/z in mass spectrum, it is seen that ethylenediamine can not make two due to space structure
A sulphur ionizes lose two electronics simultaneously.
Therefore finding out a kind of simple method with the present invention makes to realize ionization in mass spectrum for gloomy class, and has in mass spectrum good
Good response method realizes the quick detection residual for gloomy class agriculture, establishes detection residual for gloomy class agriculture in simple, quick measurement pericarp
Method.It is specific: to filter after rinsing pericarp with water and carbon dichloride to strainer, after centrifugation is stood, supernatant is sucked out, is added
The 5% ethylenediamine water-soluble liquid oscillation of EDTA, ultrasound, are detected using liquid chromatography tandem mass spectrometry, with 210.9/177 He of m/z
210.9/135 or qualitative 225/191 and 225/149.
Therefore claimed a kind of detection method of dithiocar-bamate, samples with water are impregnated to and are vortexed
It vibrates, stand, filter to take solid, impregnated to carbon dichloride and vortex oscillation, stand, filter to take solid, be centrifuged, water is sucked out
Layer, is added lysate, and filtering carries out liquid chromatography-mass spectrography/mass spectroscopy；Wherein, lysate is the EDTA2Na of 0.2~2g/L
Ethylenediamine solution.
Preferably, lysate is the ethylenediamine solution of the EDTA2Na of 1g/L.
Preferably, 6~15min of vortex oscillation stands 8~15min.
It is highly preferred that vortex oscillation 10min, stands 10min.
Preferably, 3500~4500r/min is centrifuged 2~8min.
It is highly preferred that 4000r/min is centrifuged 5min.
Preferably, by volume, water: carbon dichloride: lysate=0.5~2:0.5~1.8:0.5~2.
It is highly preferred that by volume, water: carbon dichloride: lysate=1:1:1.
Preferably, it is impregnated in two times with water and carbon dichloride.
Preferably, strainer filtering is used after standing.
Preferably, it is added after lysate through 0.22 μm of membrane filtration.
Preferably, the preparation method of the standard solution of various dithiocar-bamates to be measured are as follows: by various two sulphur to be measured
It is dissolved respectively with 1~7% ethylenediamine solution of disodium ethylene diamine tetraacetate for carbaminate, so that dithiocarbamates to be measured
The concentration of formates is 0.00008~0.0012g/mL, and the concentration of disodium ethylene diamine tetraacetate is 0.0008~0.013g/mL,
The hybrid standard working solution of suitable concentration is gradually diluted to 1~7% ethylenediamine solution；Wherein, disodium ethylene diamine tetraacetate
Mass ratio with dithiocar-bamate to be measured is (2~20): 1
Preferably, the mass ratio of disodium ethylene diamine tetraacetate and dithiocar-bamate to be measured is 10:1.
Preferably, dithiocar-bamate to be measured is in maneb, zineb, Carbatene, Propineb and Mancozeb
One or more.
Preferably, it is dissolved with 3~5% ethylenediamine solutions
Preferably, it is dissolved with 5% ethylenediamine solution.
Preferably, the concentration of dithiocar-bamate is 0.0001g/mL, and the concentration of disodium ethylene diamine tetraacetate is
0.001g/mL。
Preferably, the liquid phase chromatogram condition, chromatographic column xbridge, Waters；Mobile phase: A phase, acetonitrile；B phase surpasses
Pure water；C phase, 0.1% ethylenediamine methanol, in terms of volume, and isocratic elution 5min, A phase 10%, B phase 70%, C phase 20%,
5.00min。
Preferably, the mass spectrum/Mass Spectrometry Conditions, ion source are electric spray ion source, and scanning mode is negative ion scan, inspection
Survey mode is multiple reaction detection, and electron spray voltage is 5.500V, nebulizer pressure 0.065Mpa, and gas curtain atmospheric pressure is
0.016Mpa, assist gas pressure power are 0.060Mpa, and ion source temperature is 45 DEG C.
Preferably, the qualitative ion pair of maneb, zineb, Carbatene and Mancozeb is 210.9/135 and of m/z
210.9/177, quota ion is m/z 210.9/177, and collision voltage is -20V, and removing cluster voltage is -14V and -7V；Third
The qualitative ion pair of gloomy zinc is m/z 225/191 and 225/149, and quota ion m/z210.9/177, collision voltage is -22V,
Removing cluster voltage is -9V and -14V.
Application of the method in detection dithiocar-bamate.
Preferably, the application in detection fruits and vegetables dithiocar-bamate pesticide residue.
It is highly preferred that the fruits and vegetables are apple.
Compared with prior art, the invention has the following beneficial effects:
Currently, passing through derivatization and Solid Phase Extraction only using the method for HPLC-MS detection EBDCs both at home and abroad to detect.
The present invention dissolves EBDCs by the ethylenediamine solution of EDTA, and has good response in mass spectrum, has found EBDCs's
Non-derived detection method.Method pre-treatment is simple, without derivatization and Solid Phase Extraction, have the good rate of recovery, accuracy with
The rate of recovery.4 kinds of maneb, zineb, Mancozeb, Propineb etc. is detected for gloomy class compound in 20-2000ng/ml concentration model
Enclose interior linear scale relationships, the rate of recovery exists when related coefficient 0.9946-0.9999,10,20,100 μ g/kg of pitch-based sphere
81.40%~91.01%, relative standard deviation is between 2.89%~4.42%.Method pretreatment simple and sensitive is good, reappears
Property it is high, for the quick detection of gloomy pesticide residue suitable for pericarp.,
Detailed description of the invention
Fig. 1 is probing into for mechanism
Fig. 2 is the degree of stability of different solvents lower generation gloomy class.
Fig. 3 is influence of the EDTA2Na of various concentration to instrumental response value.
Fig. 4 is the range of linearity under 5% ethylenediamine concentration.
Fig. 5 is influence of the washing times to the rate of recovery.
Specific embodiment
The present invention is made with specific embodiment with reference to the accompanying drawings of the specification and further being elaborated, the embodiment
It is served only for explaining the present invention, be not intended to limit the scope of the present invention.Test method as used in the following examples is such as without spy
Different explanation, is conventional method；Used material, reagent etc., unless otherwise specified, for the reagent commercially obtained
And material.
Reagent:
Methanol: chromatographically pure (Guangzhou Chemical Reagent Factory)
Ethylenediamine: it analyzes pure (Guangzhou Chemical Reagent Factory)
Disodium ethylene diamine tetraacetate: it analyzes pure (Guangzhou Chemical Reagent Factory)
Carbon dichloride: it analyzes pure (Guangzhou Chemical Reagent Factory)
Mancozeb: 86.3% (State center for standard matter)
Maneb: 87.3% (State center for standard matter)
Zineb: 79.6% (State center for standard matter)
Dithane A40: 89.4% (State center for standard matter)
Propineb: 82.1% (State center for standard matter)
Key instrument equipment
Assay balance (electronic balance): Sai Duolisi scientific instrument (Beijing) Co., Ltd
3-16PK freezes desk centrifuge: Sigma-Aldrich Shanghai trade Co., Ltd
Milli-QAdvantageA10 ultrapure water system: Millipore company, the U.S.
Chromatographic column: xbridge:Waters
Liquid chromatography-tandem mass instrument: Anjelen Sci. & Tech. Inc
Assay balance (electronic balance): Sai Duolisi scientific instrument (Beijing) Co., Ltd
A kind of gloomy class Pesticides Testing method of the generation of embodiment 1
The preparation of standard solution: Mancozeb, maneb, zineb, Carbatene, Dithane A40, Propineb, prestige are weighed respectively
0.01g disodium ethylene diamine tetraacetate solid is added in 10ml volumetric flask in hundred mu of 0.001g, molten with 3% ethylenediamine solution
Solution, is settled to scale.It is appropriate accurately to draw 9 kinds of standard reserving solutions, sets in 10ml volumetric flask, gradually with 3% ethylenediamine solution
It is diluted to the hybrid standard working solution of suitable concentration.
The preparation of lysate: weighing 0.1g EDTA2Na solid in 100mL volumetric flask, and 5mL ethylenediamine solution is added, and uses
Ultrapure water is settled to 100mL.
Sample to be tested 5.0g is weighed in 50ml centrifuge tube, is impregnated twice with 20ml moisture, vortex oscillation 10min, is stood
10min uses strainer filtering；It is impregnated in two times with 20ml carbon dichloride, vortex oscillation 10min, stands 10min, use strainer filtering.
4000r/min is centrifuged 5min, water layer is sucked out, and 20ml lysate is added, and vibrates 20min.After 0.22 μm of membrane filtration, carry out
Liquid chromatography-mass spectrography/mass spectroscopy.
1) chromatographic column: xbridge, Waters；
2) mobile phase: A phase: acetonitrile；B phase: ultrapure water；C phase: 0.1% ethylenediamine methanol；
3) gradient elution program:
4) Mass Spectrometry Conditions
5) qualitative ion pair, quota ion pair, collision voltage go cluster voltage see the table below
1 Mass Spectrometry Conditions of table:
The selection of 2 solvent of embodiment
One, experimental method
It is dissolved respectively with 3% ethylenediamine solution of the 3% ethylenediamine methanol solution of EDTA and EDTA for gloomy class pesticide, and
The stability for gloomy class pesticide is investigated in 1h, 2h, 1Day and 1Week.
Two, experimental result
It the results are shown in Table 2 and Fig. 2, the 3% ethylenediamine methanol solution of EDTA can be dissolved for gloomy class as the result is shown, but Dai Sen
Class decayed to rapidly nothing in 2 hours.And stablized 60 days with being able to maintain for gloomy class in 3% ethylenediamine solution of EDTA.
Therefore select water as solvent.
Influence of 2 different solvents of table to being dissolved for gloomy class:
Influence of the different amine of embodiment 3 to the solubility for gloomy class in EDTA aqueous solution
One, experimental method
It is dissolved in EDTA aqueous solution for gloomy class with ethylenediamine, isobutyl amine, dimethylamine, ammonium hydroxide, di-n-butylamine, pyridine respectively
Pesticide, upper machine testing detect these substances to the dissolution energy for gloomy class in EDTA aqueous solution by ionizing situation for gloomy class
Power.
Two, experimental result
The results are shown in Table 3, ethylenediamine can make to ionize for gloomy class, can be by the ion that breaks into pieces in mass spectrum, other amine are not
It can make to ionize for gloomy class.Therefore select ethylenediamine as gloomy class lytic agent.
Influence of the different amine of table 3 to being dissolved for gloomy class:
Influence of the EDTA of 4 various concentration of embodiment to the response for gloomy class in mass spectrum
One, experimental method
Standard is prepared with the ratio of five kinds of different EDTA2Na: maneb such as 2:1,5:1,10:1,15:1,20:1 respectively
Solution is diluted to the various concentrations such as 10ppb, 20ppb, 50ppb, 100ppb, 200ppb, 500ppb, with 210.9/177 peak area
Quantitative determination.
Two, experimental result
It the results are shown in Table 4 and Fig. 3, the results show that the maneb standard solution of the EDTA2Na: maneb of different proportion is to instrument
The response of device influences less, and whenever EDTA2Na ratio increases, high concentration, when ratio is greater than 10:1, instrumental response value is almost
Do not change.The range of linearity can reach 10ppb~500ppb.Therefore the EDTA2Na: maneb proportional arrangement standard of 10:1 is selected
Solution.
Influence of the EDTA of 4 different quality concentration ratio of table to instrumental response value
Influence of the ethylenediamine of 4 various concentration of embodiment to the response for gloomy class in mass spectrum
One, experimental method
0%, 1%, 3%, 5% 4 kind of ethylenediamine concentration are configured, detects it to the solvability for gloomy class
Two, experimental result
It the results are shown in Table 5 and Fig. 4, the ethylenediamine of low concentration cannot make to be completely dissolved for gloomy class, and 5% ethylenediamine can make line
Property range is expanded to 20~2000ppb, therefore has selected 5% ethylenediamine concentration.
The influence that the ethylenediamine of 5 various concentration of table responds mass spectrum:
Influence of 5 washing times of embodiment to the rate of recovery
One, experimental method
Influence of the different washing times to the rate of recovery is investigated.It takes 0.0025g maneb in 25ml volumetric flask, is added
25ml water is filtered after vibrating completely with three layers of filter paper, washing capacity bottle 2 times, filtering.Configure the maneb lysate of 25ml
(0.025gEDTA2Na, 24.25ml water+0.75ml ethylenediamine), washs filter paper several times, sufficiently presses standard solution after oscillation
Dilution step dilution, upper machine.
Two, experimental result
As a result see Fig. 5, the results showed that washing can make the rate of recovery reach 80% or more 4 times, therefore select to wash 4 times as
The method of pre-treatment.
6 standard solution stability of embodiment is probed into
One, experimental method
- 4 DEG C of standard solution refrigerator of configuration or less saves, storage 10,20,30, be diluted to 10,20 again after 60days,
50,100,200,500ppb sample introductions detect its response.
Two, experimental result
The result shows that can be saved 60 in -4 DEG C or less refrigerators for gloomy class.
7 range of linearity of embodiment, regression equation, related coefficient, detection limit
One, experimental method
It is detected according to 1 method of embodiment.
Two, experimental result
It the results are shown in Table 6.
6 range of linearity of table, regression equation, related coefficient, detection limit:
8 rate of recovery of embodiment and precision
One, experimental method
0.5g blank sample is taken to carry out five kinds respectively for gloomy class compound in 3 concentration levels (10ul/kg, 20ul/
Kg, 60ul/kg) addition recovery experiment, be measured as described in Example 1, each mark-on level is repeated 6 times,
Two, experimental result
The results are shown in Table 7, the results showed that the rate of recovery between 81.40%~91.01%, relative standard deviation 2.89~
Between 4.42, meet test requirements document.
7 average recovery rate of table and precision:
The detection of 9 actual sample of embodiment
One, experimental method
Commercially available 10 kinds of apples are carried out as described in Example 1 actually detected.
Two, experimental result
It the results are shown in Table 8, each test sample meets limitation requirement.
The testing result of 8 actual sample of table:
Claims (10)
1. a kind of detection method of dithiocar-bamate, which is characterized in that samples with water impregnate to and it is vortex oscillation, quiet
It sets, filter to take solid, impregnated to carbon dichloride and vortex oscillation, stand, filter to take solid, be centrifuged, water layer is sucked out, be added molten
Liquid is solved, filtering carries out liquid chromatography-mass spectrography/mass spectroscopy；Wherein, lysate is the ethylenediamine of the EDTA2Na of 0.2~2g/ L
Solution.
2. detection method according to claim 1, which is characterized in that 6~15min of vortex oscillation stands 8~15min.
3. detection method according to claim 1, which is characterized in that 3500~4500r/min is centrifuged 2~8min.
4. detection method according to claim 1, which is characterized in that by volume, water: carbon dichloride: lysate=0.5
~2:0.5~1.8:0.5~2.
5. detection method according to claim 4, which is characterized in that impregnated in two times with water and carbon dichloride.
6. detection method according to claim 1, which is characterized in that the standard of various dithiocar-bamates to be measured is molten
The preparation method of liquid are as follows: by various dithiocar-bamates to be measured respectively with 1~7% ethylenediamine of disodium ethylene diamine tetraacetate
Aqueous dissolution, so that the concentration of dithiocar-bamate to be measured is 0.00008~0.0012g/ mL, ethylenediamine tetra-acetic acid
The concentration of disodium is 0.0008~0.013g/mL, and the hybrid standard of suitable concentration is gradually diluted to 1~7% ethylenediamine solution
Working solution；Wherein, the mass ratio of disodium ethylene diamine tetraacetate and dithiocar-bamate to be measured is (2~20): 1.
7. detection method according to claim 1, which is characterized in that the liquid phase chromatogram condition, chromatographic column are
xbridge,Waters；Mobile phase: A phase, acetonitrile；B phase, ultrapure water；C phase, 0.1% ethylenediamine methanol are in terms of volume, isocratic
Elute 5 min, A phase 10%, B phase 70%, C phase 20%, 5.00min.
8. detection method according to claim 1, which is characterized in that the mass spectrum/Mass Spectrometry Conditions, ion source are electron spray
Ion source, scanning mode are negative ion scan, and detection mode is multiple reaction detection, and electron spray voltage is 5.500 V, atomizer
Pressure is 0.065 Mpa, and gas curtain atmospheric pressure is 0.016 Mpa, and assist gas pressure power is 0.060 Mpa, and ion source temperature is 45 DEG C.
9. detection method according to claim 1, which is characterized in that maneb, zineb, Carbatene and Mancozeb
Qualitative ion pair is m/z 210.9/135 and 210.9/177, and quota ion is m/z 210.9/177, and collision voltage is equal
For -20 V, removing cluster voltage is -14 V and -7 V；The qualitative ion pair of Propineb is m/z 225/191 and 225/149, quantitative
Ion is m/z 210.9/177, and collision voltage is -22 V, and removing cluster voltage is -9 V and -14 V.
10. application of claim 1 the method in detection dithiocar-bamate, preferably thio in detection fruits and vegetables two
Application in carbaminate pesticide residue.
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| CN110208402A (en) * | 2019-05-30 | 2019-09-06 | 江苏恒生检测有限公司 | The method of extraction and the detection of metham-sodium on cucumber |
| CN110618189A (en) * | 2019-10-29 | 2019-12-27 | 广西大学 | Analysis method for rapidly detecting dithiocarbamate pesticide residues by adopting ion mobility spectrometry |
| CN110632163A (en) * | 2019-10-29 | 2019-12-31 | 广西大学 | Analysis method for rapidly detecting carbamate pesticide residues by adopting ion mobility spectrometry |
| CN111830167A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and determination of phosphine and dithiocarbamate compounds |
| CN111830165A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
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| CN111830165A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
| CN111830165B (en) * | 2020-07-22 | 2022-12-20 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
| CN112014504A (en) * | 2020-08-31 | 2020-12-01 | 河北双吉化工有限公司 | Analysis method of Dyson series |
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